US3640940A - Using ground carbon in oil phase masterbatching - Google Patents

Using ground carbon in oil phase masterbatching Download PDF

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Publication number
US3640940A
US3640940A US22646A US3640940DA US3640940A US 3640940 A US3640940 A US 3640940A US 22646 A US22646 A US 22646A US 3640940D A US3640940D A US 3640940DA US 3640940 A US3640940 A US 3640940A
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carbon
masterbatching
oil
vulcanizable
oil phase
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US22646A
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English (en)
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William W Gotshall
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Assigned to MARATHON OIL COMPANY, AN OH CORP reassignment MARATHON OIL COMPANY, AN OH CORP ASSIGNS THE ENTIRE INTEREST Assignors: MARATHON PETROLEUM COMPANY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • the present invention by intercombining certain steps of the masterbatching and carbon pulverizing processes, provides a masterbatch composition to which only accelerators and sulfur need be added prior to vulcanizing. At the same time, the invention minimizes the chances for deleterious oxygenation of the carbon surfaces and reduces the number of components and the capital investment required. Further, the present invention permits shipping the carbonaceous raw materials to a relatively inexpensive combination carbon-pulverizing and masterbatching facility which can be located at the masterbatching plant to avoid more expensive shipment of the finished carbon reinforcement agents.
  • selected coke or coal is ground under a nonoxidizing atmosphere in a fluid energy mill and particles in the desired size range are substantially continuously contacted with conventional extending oils to form a slurry which is mixed with a .water emulsion of vulcanizable elastomer and surfactant to form a masterbatch.
  • the masterbatch is ready for addition of sulfur, accelerators and other desired modifying ingredients and fabrication into finished rubber products.
  • the required apparatus omits the dust collector and coating mixer and their related inert atmosphere accessories and instead connects an oil scrubber to the outlet of the classifier to form the slurry substantially continuously and avoid significant oxygenation of the carbon surfaces.
  • the masterbatches prepared by the processes and apparatus of the present invention are useful in the manufacture of a wide variety of elastomeric products including mechanical rubber goods, tire carcasses and tread stocks, rubber extrusions, and similar materials made from vulcanizable elastomers such as natural and synthetic rubber, styrene-butadiene copolymer, butadieneacrilonitrile copolymer, butyl rubber, ethylene-propylenediolefin terpolymer, polyisoprene, vulcanizable polymeric elastomeric material containing double bonds and derived from chloroprenes or fluoroprenes.
  • vulcanizable elastomers such as natural and synthetic rubber, styrene-butadiene copolymer, butadieneacrilonitrile copolymer, butyl rubber, ethylene-propylenediolefin terpolymer, polyisoprene, vulcanizable polymeric elast
  • Carbon materials.Carbonaceous materials suitable as starting materials for the present invention include delayed petroleum coke, fluid petroleum coke, anthracite coal, coke derived from coal, char, e.g. nonagglomerating materials derived from coal or by the techniques of copending application S.N. 22,648 filed Mar. 25, 1970 (Docket 690112-A-USA).
  • the carbonaceous materials should contain from about 0.1 to about 10, more preferably from 1 to about 8, and most preferably from 2 to about 6% by weight volatile combustible matter based on the weight of carbon.
  • 25 to 150, more preferably from about 25 to about 400, more preferably 40 to 200, and most preferably from 50 to parts by weight of carbon will be employed for each part by weight of elastomer in the finished masterbatch (phr.).
  • Vulcanizable elast0mers Vulcanizable elast0mers.Vulcanizable elastomers in general may be employed, but preferred among these will be those mentioned above under Utility, and most preferred are styrene-butadiene copolymer (SBR), and butyl rubber.
  • SBR styrene-butadiene copolymer
  • Surfactanfs.-Conventional surfactants e.g. sodium lignin sulfonate or rosin acid soap which are utilized for the preparation of aqueous emulsions or vulcanizable elastomers in conventional masterbatching will be employed. About 0.25 to about 10, more preferably from about 0.5 to about 5, and most preferably from about 1 to about 3 parts of surfactant per hundred parts by weight of carbon will be employed.
  • Extender oils are utilized with the present invention in the amounts normally used when employing conventional carbon blacks in the formulations. Extending oil loadings of from to about 75, more preferably to 50, and most preferably to parts per hundred parts of elastomer (phr.), can be utilized with the present invention.
  • the ex tender oils will be of the conventional types discussed in the aforementioned text by Morton and the references cited therein, particularly in chapter 7.
  • the preferred grinding mills for pulverizing the carbonaceous material are fluid energy mills of the type commonly referred to as ,hurricane mills, e.g. the Model No. 30-10 mill manufactured by Majac, Inc. of Sharpsburg, Pa.
  • the fluid energy mills can operate on a wide variety of inert, non-oxiding atmosphere.
  • nonoxidizing atmosphere is meant herein, media which do not contain substantial quantities of free oxygen.
  • Steam is the most preferred grinding media from the standpoint of economy, but nitrogen, helium, hydrogen, argon, and a wide variety of other gases commonly thought of as inert or reducing, may be utilized.
  • gases of lower molecular weights e.g. hydrogen and steam, are preferred.
  • the autogenous grinding mill is conventionally operated, preferably at temperatures of from about 350 to about 800 F., more preferably from about 400 to about 700 F., and most preferably at 400-500 F.
  • the classifier is operated to provide an average particle size (by Weight) of less than about 2.5 microns with 99% by weight of the product having particle size of less than 5 microns. More preferred ranges are average particle size of less than 1.5 and 99% by weight less than 3 microns.
  • the classifier is preferably a centrifugal type and is operated under nonoxidizing atmosphere.
  • the scrubber can be of conventional design to provide intimate contact between the oil and the ground carbon exiting from the classifier.
  • the emulsion-slurry mixer can be of conventional design, preferably a venturi mixer to provide intimate contact between the carbon-containing oil slurry and the elastomeric emulsion.
  • Conventional filters, surge tanks, and settling tanks may be employed.
  • EXAMPLE I Referring to the drawing, a raw fluid coke produced by granulating a fluid petroleum coke of the type produced according the methods of A. Voorhies, Fluid Coking, Proceedings of the 4th World Petroleum Congress, Section III/F, page 360 and Petroleum Processing, March 1956, pages 135 to 137 is fed from bin 1 to a Model No. 30-10 mill 2, manufactured by Majac, Inc. of Sharpsburg, Pa. Steam is utilized as the grinding fluid and a sonic velocity at approximately 400 to 800 F. (after exiting from the nozzle) and 100 to 150 p.s.i.g. nozzle pressure is maintained in the grinding section of the mill.
  • This particular mill has opposed nozzles which cause a stream of particles to impinge upon a second stream of paritclesv causing highly efficient autogenous grinding.
  • This grinding process is continued with particles having an average particle size of below about 1.5 microns and 99% by weight having a particle size below about 3 microns being continuously withdrawn from the classier 3 of the Majac mill 2.
  • Oversize particles are returned to the pulverizer for further grinding through conduit 4.
  • Steam and ground carbon of the desired maximum particle size are propelled by steam pressure through conduit 5 to venturi scrubber 6 where the excess steam is exhausted through outlet 7 and the carbon particles are contacted with extender oil.
  • Approximately 2# of oil are fed to the venturi scrubber for each pound of ground carbon entering the scrubber and the oil-carbon mixture exits through outlet 8 of the scrubber as a 33% carbon oil slurry, The slurry is stirred in an agitated surge tank 10.
  • a pump 11 conveys the slurry into venturi mixer 12 where it is intimately mixed with an aqueous vulcanizable elastomeric emulsion consisting of 92-97% water, 2% sodium lignin sulfonate surfactant, and 5- 10% SBR.
  • Approximately 0.75 pound of carbon in an oil slurry are fed for each pound of vulcanizable elastomer in an aqueous emulsion.
  • the mixture exiting from the venturi mixer is then acidified to a pH in the range of 6.5 to 7.5 in order to coagulate the masterbatch from the excess water which is separated out by settling in tank 14 and filtering in filter 15. Masterbatch is then conventionally baled in baler 16 and stored until it is to be mixed with sulfur, accelerators and other ingredients and vulcanized into finished vulcanized elastomeric products.
  • a process for the manufacture of masterbatches comprising vulcanizable elastomers, together with carbon particles having surfaces substantially free from oxygenation, said process comprising in combination the steps of:
  • Col. 2 lines 63-65: Should read: -based'on the weight of carbon.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Working-Up Tar And Pitch (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
US22646A 1970-03-25 1970-03-25 Using ground carbon in oil phase masterbatching Expired - Lifetime US3640940A (en)

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US2264670A 1970-03-25 1970-03-25

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US (1) US3640940A (fr)
JP (1) JPS551301B1 (fr)
CA (1) CA926533A (fr)
FR (1) FR2084206A5 (fr)
GB (1) GB1304315A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889880A (en) * 1986-06-27 1989-12-26 The Lubrizol Corporation Modified asphalt compositions
US5427022A (en) * 1992-10-27 1995-06-27 American Tire Reclamation, Inc. Apparatus for axial compression of tires having aligning member
US8239027B2 (en) 2001-05-01 2012-08-07 Intrapace, Inc. Responsive gastric stimulator

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2216105C3 (de) * 1972-04-01 1982-03-25 Bergwerksverband Gmbh, 4300 Essen Dichtungsmaterial

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889880A (en) * 1986-06-27 1989-12-26 The Lubrizol Corporation Modified asphalt compositions
US5427022A (en) * 1992-10-27 1995-06-27 American Tire Reclamation, Inc. Apparatus for axial compression of tires having aligning member
US8239027B2 (en) 2001-05-01 2012-08-07 Intrapace, Inc. Responsive gastric stimulator

Also Published As

Publication number Publication date
GB1304315A (fr) 1973-01-24
DE2113219B2 (de) 1975-11-13
JPS551301B1 (fr) 1980-01-12
DE2113219A1 (de) 1971-10-14
CA926533A (en) 1973-05-15
FR2084206A5 (fr) 1971-12-17

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Owner name: MARATHON OIL COMPANY, AN OH CORP

Free format text: ASSIGNS THE ENTIRE INTEREST IN ALL PATENTS AS OF JULY 10,1982 EXCEPT PATENT NOS. 3,783,944 AND 4,260,291. ASSIGNOR ASSIGNS A FIFTY PERCENT INTEREST IN SAID TWO PATENTS AS OF JULY 10,1982;ASSIGNOR:MARATHON PETROLEUM COMPANY;REEL/FRAME:004172/0421

Effective date: 19830420